JPH0632895A - Production of polyaryl ether - Google Patents

Abstract

PURPOSE:To reproducibly produce a high-molecular polyaryl ether excellent in heat resistance and mechanical strength in a short time. CONSTITUTION:This polyaryl ether is produced by polycondensing a dihalogenodiphenyl compound with a divalent phenol compound in the presence of a granular alkaline metal compound exhibiting >=0.3m<2>/g specific surface area in an organic polar solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high molecular weight polyaryl ether having excellent heat resistance and mechanical strength with good reproducibility and in a short time.

[0002]

2. Description of the Related Art Polyaryl ethers are obtained by reacting a dihydric phenol, an alkali metal compound and a dihalogenodiphenyl compound in an organic polar solvent,
In the reaction system, synthesize an alkali metal di-salt of dihydric phenol,
Alternatively, it is known that an alkali metal disalt of a dihydric phenol is previously synthesized, and a polyhalogenation reaction is performed with a dihalogenodiphenyl compound in an organic polar solvent to produce the salt. (Japanese Patent Publication No. 42-7799, Japanese Patent Publication No. 45-21318, and Japanese Patent Laid-Open No. 48-19700). The amount of the alkali metal compound used in the above polycondensation reaction is preferably a stoichiometric amount of the alkali metal atom with respect to the hydroxyl group of the dihydric phenol compound, or a very slight excess, and the alkali metal atom is If the amount is less than the stoichiometric amount, a high molecular weight polyaryl ether having high heat resistance and mechanical strength of the molded article cannot be obtained. Therefore, in order to produce a high molecular weight polyaryl ether in a short time in a polycondensation reaction with good reproducibility, it is desired to establish a method for producing a polyaryl ether that effectively uses an alkali metal compound.

[0003]

The inventors have found that the specific surface area of the alkali metal compound in the raw material used in the reaction is
It was found that this is one of the factors for producing a high-molecular-weight polyaryl ether with good reproducibility in a short time. The present invention has been completed based on this finding.

In the present invention, in the presence of an alkali metal compound,
In the method for producing a polyaryl ether by polycondensing a dihalogenodiphenyl compound and a dihydric phenol compound in an organic polar solvent, it is preferable to use particles having a specific surface area of 0.3 m ² / g or more as an alkali metal compound. It relates to a method for producing a characteristic polyaryl ether.

The alkali metal compound used in the present invention includes alkali metal carbonates, alkali metal hydroxides,
Examples thereof include alkali metal hydrides and alkali metal alkoxides. Particularly, sodium carbonate and potassium carbonate are preferable.

In the present invention, as the alkali metal compound, particles having a specific surface area of 0.3 m ² / g or more, preferably 0.4 m ² / g or more are used. When the specific surface area of the particles of the alkali metal compound is small at 0.3 m ² / g, it is not possible to produce a high molecular weight polyaryl ether because the necessary amount of the alkali metal compound is not supplied in the polycondensation reaction, and the polymerization rate is also high. Also decreases.

The alkali metal compound is added before the polycondensation reaction.
60 to 500 in advance in an inert gas such as nitrogen gas
You may use what was heat-processed for 1 minute or more under (degreeC), normal pressure, or pressure reduction.

The organic polar solvent in the present invention is not particularly limited as long as it dissolves the produced polymer at the polycondensation temperature. For example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, N-methyl-2-pyrrolidone and N-vinyl-2.
-Pyrrolidone-based solvents such as pyrrolidone, N-methyl-2
-Piperidone-based solvents such as piperidone, 1,3-dimethyl-2-imidazolinone, 2-imidazolinone-based solvents such as 1,3-diethyl-2-imidazolinone, hexamethylene sulfoxide, γ-butyrolactone, sulfolane, or Examples thereof include diphenyl compounds such as diphenyl ether and diphenyl sulfone. In particular, N-methyl-2-pyrrolidone and N, N-dimethylacetamide are preferably used because they are also excellent in reducing coloration.

The dihalogenodiphenyl compound is represented by the general formulas (I) and (II)

[0011]

(I) (I) (In the formula, X and X ′ are the same or different halogen atoms.)

[0012]

Embedded image (I
I) (In the formula, X and X ′ are the same or different halogen atoms.).

As a specific example, as a dihalogenodiphenyl compound, 4,4'-dichlorodiphenisulfone,
4,4'-difluorodiphenyl ketone and 4,4'-
Examples thereof include difluorodiphenyl sulfone.

As the dihydric phenol compound, the following general formula (III)

(II) (II
I) (N represents 1 or 2), bis (hydroxyphenyl) alkanes, dihydroxydiphenylsulfones, dihydroxydiphenyl ethers, or the like, in addition to hydroquinone, catechol, resorcin, 4,4′-piphenol represented by And a lower alkyl group such as a methyl group, an ethyl group or a propyl group, or a lower alkoxy group such as a methoxy group or an ethoxy group.

Alternatively, two or more kinds of the above dihydric phenol compounds may be mixed and used.

The dihydric phenol compound is generally used in a substantially equimolar amount with the dihalogenodiphenyl compound, but in order to control the molecular weight of the polyaryl ether, a slight excess or an excessively small amount is used. May be used in. For this purpose, a small amount of monohalogenodiphenyl compound or monohydric phenol compound can be added to the polymerization solution.

The polycondensation temperature is usually 140 to 340 ° C. Water produced as a by-product during the reaction is preferably distilled out of the system together with an inert gas stream or an azeotropic dehydrating agent in order to produce a high molecular weight polyaryl ether. Examples of azeotropic dehydrating agents include benzene, toluene, xylene, and aromatic halogen compounds. At the end of the polycondensation, a methylating agent such as chloromethane may be added to the reaction solution as a polymer terminal stopper at 90 to 150 ° C.

The inorganic solid such as the alkali metal compound or the alkali metal halide remaining in the reaction solution can be separated by filtering or centrifuging the reaction solution. After separating the inorganic solid contained in the reaction solution by filtration or centrifugation, or without separating the inorganic solid, a poor solvent can be added to the reaction solution to separate the polyaryl ether as a precipitated solid. .

Examples of the poor solvent for the polyaryl ether include alcohols such as methanol, ethanol, isopropanol and butanol, nitriles such as acetonitrile, water and the like. Further, two or more kinds of the above compounds can be mixed and used. Further, the poor solvent may contain a good solvent for the polymer such as the above-mentioned polymerization reaction solvent, within the range where the polymer can be precipitated.

The precipitated solid is washed with a poor solvent and then dried to obtain a polyaryl ether powder.

[0021]

According to the present invention, by using particles having a specific surface area of 0.3 m ² / g or more as an alkali metal compound, a high molecular weight polyaryl ether excellent in heat resistance and mechanical strength can be obtained. It can be manufactured with good reproducibility and in a short time.

[0022]

EXAMPLES Examples of the present invention will be described below. The reduced viscosities η _{sp / c} in the examples and comparative examples are represented by the following equation. η _{sp / c} = (t−t ₀ ) / t ₀ / c where t is the transit time (seconds) between the marked lines of the polymer solution in the viscometer, and t ₀ is the measured _value between the marked lines in the viscometer of the pure solvent. The passage time (second) and c represent the concentration of the polymer solution (g / 100 ml solvent). Viscosity is measured at 30 ° C, N-methyl-2-
Using a pyrrolidone solvent, the concentration of the polymer solution was 0.5 g /
It was performed with 100 ml. The specific surface area was measured using a flow type automatic specific surface area measuring device, Micromeritics Flow Soap Model 2300 (manufactured by Shimadzu Corporation).

Example 1 73.3 g of 4,4'-dichlorodiphenyl sulfone, 13.7 g of hydroquinone and 4,4'-biphenol 2
3.2 g of azeotropic toluene 30 m under nitrogen atmosphere
1 and N-methyl-2-pyrrolidone (300 ml) were added and dissolved, and then 37.9 g of potassium carbonate (specific surface area 0.50 m ^{2 /} g) which was heat-treated in nitrogen at 70 ° C. for 30 minutes,
Under a nitrogen atmosphere, the mixture was reacted with stirring at a temperature of 180 ° C. for 8 hours to obtain a polymerization solution. After completion of the reaction, in order to separate the inorganic substance from the polymerization solution, the polymerization solution was obtained by filtering at a nitrogen pressure of 1.5 kg / m ² . 300 g of the polymerization solution was poured into 2000 ml of ethanol to precipitate the polymer while stirring at 5000 rpm.
A polymer was obtained after filtration and separation. After washing 50 g of this polymer with 500 ml of ethanol, it was dried at 90 ° C. to obtain a powder of polyether sulfone. The reduced viscosity (ηsp / c) of the obtained polyether sulfone was 0.52.

Example 2 The procedure of Example 1 was repeated, except that potassium carbonate having a specific surface area of 0.70 m ² / g was used. Reduced viscosity (ηsp / c) of the obtained polyether sulfone
Was 0.53.

Comparative Example 1 The procedure of Example 1 was repeated except that potassium carbonate having a specific surface area of 0.26 m ² / g was used. Reduced viscosity (ηsp / c) of the obtained polyether sulfone
Was 0.30.

Comparative Example 2 The procedure of Example 1 was repeated, except that potassium carbonate having a specific surface area of 0.18 m ² / g was used. Reduced viscosity (ηsp / c) of the obtained polyether sulfone
Was 0.26.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeru Yamamoto 8-1 Goi Minami Kaigan, Ichihara City, Chiba Ube Industries Ltd. Chiba Research Institute

Claims (1)

[Claims] 1. A method for producing a polyaryl ether by polycondensing a dihalogenodiphenyl compound and a dihydric phenol compound in an organic polar solvent in the presence of an alkali metal compound, wherein the specific surface area of the alkali metal compound is 0.3.
A method for producing a polyaryl ether, which comprises using particles having m ² / g or more.